Photoresist compositions and methods for fabricating semiconductor devices using the same

ABSTRACT

Provided herein are photoresist compositions and methods for fabricating semiconductor devices using the same. A photoresist composition may include an organometallic material, a fluorine-containing material, and an organic solvent.

FIELD

The disclosure herein relates to photoresist compositions and methodsfor fabricating semiconductor devices using the same.

BACKGROUND

Semiconductor devices have been highly integrated. Thus, finer and moreprecise patterning is needed in preparing semiconductor devices.Accordingly, an exposure process using extreme ultraviolet (EUV) havinga wavelength of 13.4 nm as a light source has been utilized. The EUV isabsorbed entirely in a conventional photoresist film due to a very shortwavelength thereof, which makes forming a precise pattern difficult.Therefore, in a photolithography process using EUV as a light source, anew photoresist material capable of transmitting the EUV may be usefulto allow for precise and fine patterning.

SUMMARY

The present disclosure provides a photoresist composition capable ofproviding a precise pattern.

The present disclosure also provides a method for fabricating asemiconductor device that is capable of forming a precise pattern.

An embodiment of the inventive concepts provides a photoresistcomposition including: an organometallic material; a fluorine-containingmaterial; and an organic solvent.

In an embodiment of the inventive concepts, a method for fabricating asemiconductor device includes: providing a photoresist compositionincluding an organometallic material, a fluorine-containing material,and an organic solvent; forming a photoresist film by coating asubstrate with the photoresist composition, wherein the photoresist filmincludes a photosensitive film and a moisture barrier layer positionedon the photosensitive film, wherein the photosensitive film comprisesthe organometallic material and the moisture barrier layer comprises thefluorine-containing material; evaporating the organic solvent through asoft bake process; converting a portion of the photosensitive film intoa mask pattern through an exposure process and a post bake process; andremoving the photosensitive film and leaving the mask pattern through adevelopment process.

In an embodiment, a method for fabricating a semiconductor deviceincludes: forming a photosensitive film and a moisture barrier layersequentially stacked on a substrate; converting a portion of thephotosensitive film into a mask pattern through an exposure process anda post bake process; and removing the photosensitive film and leavingthe mask pattern through a development process.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying drawings are included to provide a furtherunderstanding of the inventive concepts, and are incorporated in andconstitute a part of this specification. The drawings illustrateexemplary embodiments of the inventive concepts and, together with thedescription, serve to explain principles of the inventive concepts.

FIG. 1 is a flowchart showing a method for fabricating a semiconductordevice according to an example embodiment of the inventive concepts.

FIGS. 2A to 2F are cross-sectional views sequentially illustratingprocesses of a method for fabricating a semiconductor device accordingto an example embodiment of the inventive concepts.

DETAILED DESCRIPTION

Hereinafter, exemplary embodiments of the inventive concepts will bedescribed in detail with reference to the accompanying drawings.

As used herein, “and/or” refers to and encompasses any and all possiblecombinations of one or more of the associated listed items, as well asthe lack of combinations when interpreted in the alternative (“or”).

FIG. 1 is a flowchart showing a method for fabricating a semiconductordevice according to an example embodiment of the inventive concepts.FIGS. 2A to 2F are cross-sectional views sequentially illustratingprocesses of a method for fabricating a semiconductor device accordingto an example embodiment of the inventive concepts.

Referring to FIGS. 1 and 2A, a substrate 1 is prepared. The substrate 1may be, for example, a silicon single crystal wafer or a silicon oninsulator (SOI) substrate. An etching target film 3 may be formed on thesubstrate 1. The etching target film 3 may be, for example, aninsulation film; a polysilicon film such as a silicon oxide film, asilicon oxynitride film or a silicon nitride film; or a conductive filmsuch as a metal-containing film.

Subsequently, a photoresist composition is prepared or provided (S10).The photoresist composition includes a fluorine-containing material, anorganometallic material, and an organic solvent. In the photoresistcomposition, the organometallic material may be present in an amount of0.1-99 wt. % of the photoresist composition. In some embodiments, theorganometallic material may be present in the photoresist composition inan amount of 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or50% to 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% by weight ofthe photoresist composition. The fluorine-containing material may bepresent in an amount of 0.1-30 wt. % of the photoresist composition. Insome embodiments, the fluorine-containing material may be present in thephotoresist composition in an amount of 0.1%, 1%, 5%, 10%, or 15% to20%, 25%, or 30% by weight of the photoresist composition. The organicsolvent may be present in an amount of 0.9-99.8 wt. % of thecomposition. In some embodiments, the organic solvent may be present inthe photoresist composition in an amount of 1%, 5%, 10%, 15%, 20%, 25%,30%, 35%, 40%, 45%, or 50% to 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%,95%, or 99% by weight of the photoresist composition. The photoresistcomposition may be used for a photolithography process using an EUVlight source.

The fluorine-containing material may include at least one functionalgroup selected from: —CFOH, —CHCFOH, —CHCFCFOH, —C(CF)OH, —CFCF(CF)OH,and/or —CHC(CF)OH.

The fluorine-containing material may be a fluorine-containing polymermaterial. The fluorine-containing polymer material may have a structurerepresented by one of formula (1) to (14) below.

In formulae (1) to (14), a, b and c, when present, may eachindependently be a natural number such as, for example, a natural numberfrom 1 to 100 or 1 to 50.

In formulae (1) to (14), R¹, if present, may each be fluorine. Informulae (7) to (9) and (11) to (14), R², if present, may eachindependently be a hydrogen or a hydrophilic group (e.g., a polargroup). The hydrophilic group may comprise a carboxyl group, a hydroxylgroup and/or an amine. The hydrophilic group may be able to absorbmoisture through hydrogen bonding with water. In formulae (11) to (14),R³, if present, may each independently be a hydrophobic group or anon-polar group. The non-polar group may allow for the moisture barrierlayer 5 b to be dissolved well in a developer during a developmentprocess. R³ in formulae (11) to (14) may comprise at least one metalsuch as, e.g., tin (Sn), indium (In) and/or hafnium (Hf). When R³includes a metal, EUV absorptivity of the photosensitive film 5 a may beincreased, optionally compared to absorptivity of a photosensitive filmnot in accordance with the present inventive concepts, thereby improvingsensitivity of the photosensitive film 5 a.

In formulae (7) to (10), a/(a+b) may be 0.1-1 and b/(a+b) may be0.0-0.9. In formulae (11) to (14), a/(a+b+c) may be 0.0-0.9, b/(a+b+c)may be 0.1-1, and c/(a+b+c) may be 0.0-0.9.

In some embodiments, the fluorine-containing polymer material mayinclude: an acrylate; a methacrylate such as, e.g., shown in formula(1); and/or a methyl methacrylate (e.g., as shown in formula (2)) as amonomer or a polymer backbone. In some embodiments, thefluorine-containing polymer material may include polyhydroxy acrylate(PHS) as a monomer as shown, e.g., in formula (3). Thefluorine-containing polymer material may include a cyclic fluoroalcoholmaterial as a monomer as shown, e.g., in formulae (4) and/or (5). Insome embodiments, the fluorine-containing polymer material may include amethacrylate, to which a cyclic fluoroalcohol is bonded, as a monomer asshown, e.g., in formula (6). In some embodiments, thefluorine-containing polymer material may include combinations of two ormore monomers having a structure selected from formulae (1) to (6) asshown, e.g., in formulae (7) to (12).

The organometallic material may be an organometallic nano-clustermaterial. The organometallic material may include at least one of tin(Sn), indium (In), antimony (Sb) and hafnium (Hf). In some embodiments,the organometallic material may have a chemical formula selected fromformulae (15) to (17) below.

R_(w)MeO_((2−(w−2)−(x/2)))(OH)_(x)  (15)

R_(y)MeL_(4−y)  (16)

RMeO_((3/2−z/2))(OH)_(z)  (17)

In formulae (15) to (17), R may be a hydrocarbon compound having 1 to 30carbon atoms and containing at least one atom selected from carbon,nitrogen and oxygen. In formulae (15) to (17), Me may be at least one oftin (Sn), indium (In), antimony (Sb) and hafnium (Hf). In formula (15),0<w≤2 and 0<(w+x)≤4. In formula (16), y may be 1 or 2, and L may be ametal ligand. In formula (17), 0<z<3.

The organic solvent may be at least one of methyl isobutyl carbinol(MIBC), ether, propylene glycol monomethylether acetate (PGMEA),propylene glycol monomethylether (PGME), ethyl lactate (EL), andβ-hydroxy β-methylbutyric acid (HBM).

The photoresist composition may further include a surfactant. When theorganometallic material is present in the photoresist composition in ahigh amount, coating failure may occur in the coating step (S20) of FIG.1 for the photoresist composition. In this case, a surfactant mayimprove coating performance of the photoresist composition. Examplesurfactants include, but are not limited to, commercially availablesurfactants such as, e.g., sulfinol series of Airproduct Co. or F-series(F-410, F-444, F-477, R-08, R-30, etc.) of DIC (Dainippon Ink andChemicals, Incorporated). A surfactant may be present in the photoresistcomposition in an amount of 0-3 wt. % with respect to the total weightof the photoresist composition. In some embodiments, the surfactant maybe included in an amount of 0.2-0.8 wt. % of the photoresistcomposition. When the amount of the surfactant is more than 3 wt. % ofthe photoresist composition, it may increase a possibility that the filmquality of the photoresist film becomes poor.

In some embodiments, the photoresist composition may include a moistureabsorbent in an amount of 0-10 wt. % of the photoresist composition. Themoisture absorbent may contain an amine or a super absorbent polymer.Example moisture absorbents include, but are not limited to,polyoxyethylene nonylphenolether, R⁵C₆H₄C(CH₂CH₂O)_(n)H, polyethyleneglycol (PEG), HO(CH₂CH₂O)_(n)H and/or polyacrylamide, wherein R⁵ may bea hydrocarbon compound having 1 to 30 carbon atoms and containing atleast one atom selected from carbon, nitrogen and oxygen and n is anatural number from 1 to 1000. The moisture absorbent may capturemoisture, in some embodiments an excessive amount of moisture, in theair permeated into the photoresist film (reference numeral 5 in FIGS. 2Aand 2B), so that the moisture absorbent may suppress or prevent areaction between moisture and the organometallic material in thephotosensitive film (reference numeral 5 a in FIG. 2B).

According to some embodiments, preparing a photoresist composition mayinclude mixing a fluorine-containing material, an organometallicmaterial and an organic solvent. Preparing the photoresist compositionmay further include adding a surfactant, water and/or a moistureabsorbent. In some embodiments, at least one of a surfactant, water andmoisture absorbent are added to the photoresist composition.

Referring to FIGS. 1, 2A and 2B, a photoresist film 5 including aphotosensitive film 5 a and a moisture barrier layer 5 b may be formedby coating a substrate 1 with the photoresist composition (S20).Specifically, a photoresist film 5 may be formed by coating the etchingtarget film 3 above the substrate 1 with the photoresist composition.The photoresist film 5 may be formed to have a thickness of 1.5 nm-55nm. The fluorine-containing material contained in the photoresistcomposition has a low surface energy due to the fluorine-containingmonomer and, accordingly, the fluorine-containing material may move toan upper portion in the photoresist film 5 after coating. Accordingly,the moisture barrier layer 5 b comprising the fluorine-containingmaterial may be formed. The moisture barrier layer 5 b may also bereferred to as a fluorine-containing self-assembled moisture barrierlayer.

The organometallic material contained in the photoresist composition maybe positioned under the moisture barrier layer 5 b, and may constitutethe photosensitive film 5 a. The photosensitive film may have athickness of 1 nm-30 nm. The moisture barrier layer 5 b may have athickness of 0.5 nm-25 nm.

Referring to FIGS. 1 and 2B, a soft bake process is performed (S30),whereby the organic solvent, which may be present in the photoresistfilm 5 may be evaporated. Accordingly, the photoresist film 5, whichincludes the photosensitive film 5 a and the moisture barrier film 5 b,may become close to a solid state.

Referring to FIGS. 1 and 2C, an exposure process is performed (S40). Theexposure process may be performed using an EUV light source and aphotomask 7. In the exposure process, light (for example, EUV) that hasbeen passed through the photomask 7 may be transmitted through themoisture barrier layer 5 b, and may be incident into the photosensitivefilm 5 a, whereby the photosensitive film 5 a may have an exposedportion Sal and a non-exposed portion 5 a 2. A bond between a metal andat least one ligand of the organometallic material may be broken due tothe incident light at the exposed portion Sal of the photosensitive film5 a, thereby forming a dangling bond. Accordingly, the organometallicmaterial may comprise dangling bonds. This phenomenon does not occur inthe non-exposed portion 5 a 2 of the photosensitive film 5 a. When thefluorine-containing material constituting the moisture barrier layer 5 bcontains a metal (e.g., when the fluorine-containing material has astructure represented by one of formula (11) to (14) and R³ in formula(11) to (14) contains a metal), electrons may be emitted from the metal(e.g., the metal contained in R³) by the incident light in the exposureprocess. The emitted electrons may move to the exposed portion Sal ofthe photosensitive film 5 a to increase EUV absorptivity, therebyimproving the sensitivity of the photosensitive film 5 a.

Subsequently, referring to FIGS. 1 and 2D, a post bake process may beperformed (S50). In the post bake process, a hydroxyl group (—OH)present in the photoresist film 5 (e.g., from water) may be combinedwith the dangling bonds by heat to combine the organometallic materials,thereby providing a crosslinking reaction. Alternatively or in addition,at this time, the organometallic materials having the dangling bonds maybe combined with each other, thereby providing a crosslinking reaction.Thus, the exposed portion Sal of the photosensitive film 5 a may beconverted into a mask pattern M1.

Referring to FIGS. 1 and 2E, a development process is performed (S60),whereby the non-exposed portion 5 a 2 of the photosensitive film 5 a maybe removed. At this time, the moisture barrier layer 5 b may also besimultaneously removed. A developer used in the development process maybe n-butyl acetate and/or 2-heptanone. The fluorine-containing materialpresent in the moisture barrier layer 5 b may dissolve well in thedeveloper because of a non-polar group in the fluorine-containingmaterial. Accordingly, only the mask pattern M1 may be left on theetching target film 3.

Subsequently, referring to FIG. 2F, a desired pattern 3 a may be formedby etching the etching target film 3 using the mask pattern M1 as anetching mask.

The coating step (S20) with the photoresist composition, the soft bakeprocess (S30) and the exposure process (S40) may each be performed underan atmosphere containing moisture in a predetermined amount such as, forexample, atmosphere containing moisture in an amount of about 45%.

A method for fabricating a semiconductor device of the present inventiveconcepts uses a photoresist composition including a fluorine-containingmaterial. Since fluorine contained in the fluorine-containing materialexhibits strong hydrophobicity and/or liquid repellency, it may preventor reduce moisture contained in the air from permeating into thephotosensitive film 5 a. A hydrophilic group present in thefluorine-containing material may capture moisture (e.g., an excessiveamount of moisture) permeated into the photoresist film 5, which maythereby prevent or reduce the organometallic material present in thephotosensitive film 5 a from reacting with moisture or reduce itsreaction with moisture. When the organometallic material reacts with anexcessive amount of moisture, a condensation reaction may occur to forma metal oxide, which may not be dissolved in the developer and may makeit difficult to form a precise pattern. However, in the presentinventive concepts, it may be possible to improve this limitation byusing a photoresist composition of the present inventive concepts, and aprecise pattern formation may be realized.

Since the photoresist compositions of the present inventive concepts arenot a chemically amplified photoresist, image degradation due todiffusion of acid, which is a limitation of a chemically amplifiedphotoresist, does not occur and as such a precise pattern may be formed.Furthermore, the photoresist compositions of the present inventiveconcepts have excellent etching resistance because of an organometallicmaterial contained in the photoresist composition, so that an etchingprocess may be possible even with a thin thickness. Therefore, in someembodiments, since the photoresist film 5 may be formed having a thinthickness, a precise pattern may be formed by the EUV light source. Thephotoresist compositions according to embodiments of the presentinventive concepts may increase moisture stability because of thefluorine-containing material contained in the photoresist composition.

According to some example embodiments of inventive concepts, aphotoresist composition may include an organometallic material so thatan etch resistance of a photoresist layer may increase. In someembodiments, the photoresist composition may include afluorine-containing material so that moisture stability of a photoresistlayer may increase. Thus, it is possible to form a precise pattern byEUV light source.

According to some example embodiments of inventive concepts, a method offabricating a semiconductor device employs the photoresist composition.Thus, it is possible to form a precise pattern.

Although the exemplary embodiments of the present invention have beendescribed, it is understood that the present invention should not belimited to these exemplary embodiments but various changes andmodifications can be made by one ordinary skilled in the art within thespirit and scope of the present invention as hereinafter claimed.

What is claimed is:
 1. A photoresist composition, comprising: anorganometallic material; a fluorine-containing material; and an organicsolvent.
 2. The photoresist composition of claim 1, wherein theorganometallic material is an organometallic nano-cluster material, andwherein the fluorine-containing material is a fluorine-containingpolymer material.
 3. The photoresist composition of claim 1, wherein theorganometallic material is present in the photoresist composition in anamount of 0.1-99 wt. % of the photoresist composition, thefluorine-containing material is present in the photoresist compositionin an amount of 0.1-30 wt. % of the photoresist composition, and theorganic solvent is present in the photoresist composition in an amountof 0.9-99.8 wt. % of the photoresist composition.
 4. The photoresistcomposition of claim 1, wherein the organometallic material comprises atleast one metal selected from the group consisting of: tin (Sn), indium(In), antimony(Sb), and hafnium (Hf).
 5. The photoresist composition ofclaim 1, wherein: the fluorine-containing material has a structurerepresented by one of formula (1) to (14):

wherein: a, b and c, if present, are each independently a naturalnumber; R¹, if present, is fluorine; R², if present, is eachindependently hydrogen or a hydrophilic group; and R³, if present, is ahydrophobic group; and wherein, in formulae (7) to (10), a/(a+b) is0.1-1 and b/(a+b) is 0.0-0.9; and wherein, in formulae (11) to (14),a/(a+b+c) is 0.0-0.9, b/(a+b+c) is 0.1-1, and c/(a+b+c) is 0.0-0.9. 6.The photoresist composition of claim 1, wherein the fluorine-containingmaterial comprises at least one functional group selected from the groupconsisting of —CFOH, —CHCFOH, —CHCFCFOH, —C(CF)OH, —CFCF(CF)OH, and—CHC(CF)OH.
 7. The photoresist composition of claim 1, wherein theorganic solvent comprises methyl isobutyl carbinol (MIBC), ether,propylene glycol monomethylether acetate (PGMEA), propylene glycolmonomethylether (PGME), ethyl lactate (EL), and/or β-hydroxyβ-methylbutyric acid (HBM).
 8. The photoresist composition of claim 1,further comprising a surfactant in an amount of 0.01-3 wt. % of thephotoresist composition.
 9. The photoresist composition of claim 1,wherein the organometallic material has a chemical formula representedby one of formula (15) to (17):,R_(w)MeO_((2−(w−2)−(x/2)))(OH)_(x)  (15)R_(y)MeL_(4−y)  (16)RMeO_((3/2−z/2))(OH)_(z)  (17) wherein: R is a hydrocarbon compoundhaving 1 to 30 carbon atoms and includes at least one atom selected fromcarbon, nitrogen and oxygen, Me is selected from the group consistingof: tin (Sn), indium (In), antimony (Sb), and hafnium (Hf); and wherein,in formula (15), 0<w≤2 and 0<(w+x)≤4, in formula (16), y is 1 or 2, andL is a metal ligand, and, in formula (17), 0<z<3.
 10. The photoresistcomposition of claim 1, further comprising a moisture absorbent in anamount of 0.01-10 wt. % of the photoresist composition.
 11. Thephotoresist composition of claim 10, wherein the moisture absorbent isselected from the group consisting of polyoxyethylene nonylphenolether,R⁵C₆H₄C(CH₂CH₂O)_(n)H, polyethylene glycol (PEG), HO(CH₂CH₂O)_(n)H, andpolyacrylamide, wherein R⁵ is a hydrocarbon compound having 1 to 30carbon atoms and includes at least one atom selected from carbon,nitrogen and oxygen and n is a natural number selected from 1 to 1,000.12. The photoresist composition of claim 1, further comprising water inan amount of 0.001-0.1 wt. % of the photoresist composition.
 13. Amethod for fabricating a semiconductor device, the method comprising:providing a photoresist composition including an organometallicmaterial, a fluorine-containing material, and an organic solvent;forming a photoresist film by coating a substrate with the photoresistcomposition, wherein the photoresist film includes a photosensitive filmand a moisture barrier layer on the photosensitive film, wherein thephotosensitive film comprises the organometallic material and themoisture barrier layer comprises the fluorine-containing material;evaporating the organic solvent using a soft bake process; converting aportion of the photosensitive film into a mask pattern using an exposureprocess and a post bake process; and removing the photosensitive filmand leaving the mask pattern using a development process.
 14. The methodof claim 13, further comprising removing the moisture barrier layerusing the development process.
 15. The method of claim 13, wherein thedevelopment process is performed using n-butyl acetate or 2-heptanone.16. The method of claim 13, wherein the photosensitive film has athickness of 1 nm-30 nm, and the moisture barrier layer has a thicknessof 0.5 nm-25 nm.
 17. A method for fabricating a semiconductor device,the method comprising: forming a photosensitive film and a moisturebarrier layer on a substrate, wherein the photosensitive film and themoisture barrier layer are sequentially stacked on the substrate;converting a portion of the photosensitive film into a mask patternusing an exposure process and a post bake process; and removing thephotosensitive film and leaving the mask pattern using a developmentprocess.
 18. The method of claim 17, wherein forming the photosensitivefilm and the moisture barrier layer on the substrate comprises:providing a photoresist composition including an organometallicmaterial, a fluorine-containing material, and an organic solvent; andforming a photoresist film by coating the substrate with the photoresistcomposition, wherein the photoresist film includes the photosensitivefilm and the moisture barrier layer, and wherein the photosensitive filmcomprises the organometallic material and the moisture barrier layercomprises the fluorine-containing material.
 19. The method of claim 18,further comprising, prior to the exposure process, evaporating theorganic solvent from the photoresist film using a soft bake process. 20.The method of claim 17, wherein the moisture barrier layer is removedusing the development process.